CN114655987A - Method for producing mangano-manganic oxide and co-producing lead-silver alloy - Google Patents
Method for producing mangano-manganic oxide and co-producing lead-silver alloy Download PDFInfo
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- CN114655987A CN114655987A CN202111657320.0A CN202111657320A CN114655987A CN 114655987 A CN114655987 A CN 114655987A CN 202111657320 A CN202111657320 A CN 202111657320A CN 114655987 A CN114655987 A CN 114655987A
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- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 229910001316 Ag alloy Inorganic materials 0.000 title claims abstract description 12
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 title claims abstract description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 29
- 239000011572 manganese Substances 0.000 claims abstract description 29
- 239000002893 slag Substances 0.000 claims abstract description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 17
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 16
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 16
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 15
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000012528 membrane Substances 0.000 claims abstract description 11
- 239000000919 ceramic Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 8
- 238000003825 pressing Methods 0.000 claims abstract description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 7
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 7
- 239000004571 lime Substances 0.000 claims abstract description 7
- 239000008267 milk Substances 0.000 claims abstract description 7
- 210000004080 milk Anatomy 0.000 claims abstract description 7
- 235000013336 milk Nutrition 0.000 claims abstract description 7
- 238000004806 packaging method and process Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 230000008020 evaporation Effects 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000001694 spray drying Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000002386 leaching Methods 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 23
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 14
- 239000002699 waste material Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000005086 pumping Methods 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 9
- 239000000571 coke Substances 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 241001062472 Stokellia anisodon Species 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 239000002918 waste heat Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 238000011085 pressure filtration Methods 0.000 claims description 2
- 239000000779 smoke Substances 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 6
- 239000000839 emulsion Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/022—Preparation of aqueous ammonia solutions, i.e. ammonia water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C11/00—Alloys based on lead
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Ceramic Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- Structural Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
A method for producing trimanganese tetroxide and co-producing lead-silver alloy comprises the steps of leaching electrolytic manganese anode slag with sulfuric acid and hydrogen peroxide for reaction to generate a manganese sulfate solution, and performing filter pressing to remove lead-rich slag for later use. Filtering the filtrate by a ceramic membrane, adding industrial manganese dioxide, stirring, slowly adding concentrated ammonia water, reacting for two hours, heating to 60 ℃, filtering, washing filter residues by water, spray drying, demagnetizing and packaging to obtain a finished product of trimanganese tetroxide, adding lime milk into the filtrate to deaminate to prepare ammonia water, carrying out dense filter pressing and drying on the emulsion to generate calcium sulfate solid, drying, crushing, packaging and selling, and carrying out multiple-effect evaporation on the filtrate to prepare deionized water for the previous process steps. The method realizes the high-valued comprehensive utilization of the electrolytic manganese anode slag and promotes the high-quality development of the manganese industry through the research on the electrolytic manganese production process.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a method for producing trimanganese tetroxide and co-producing lead-silver alloy.
Background
The electrolytic manganese anode slag is derived from byproducts of a wet-process electrolytic manganese production process, and about 0.1 ton of anode slag is generated per ton of electrolytic manganese produced, and the main components of the anode slag are manganese dioxide, ammonium sulfate, lead oxide, lead sulfate and the like. Belongs to hazardous waste. At present, most enterprises are handed to solid waste treatment centers for treatment. How to utilize the manganese alloy with high value is a target pursued by each electrolytic manganese production enterprise.
Disclosure of Invention
In order to solve the technical problems in the prior art, there is a need for a method for producing trimanganese tetroxide and co-producing lead-silver alloy.
The method for producing the trimanganese tetroxide and the co-production of the lead-silver alloy is characterized by comprising the following steps:
(1) obtaining electrolytic manganese anode slag, and mixing the anode slag with the solid-liquid ratio of 1: 10, adding deionized water to prepare slurry, adding concentrated sulfuric acid and hydrogen peroxide to enable the molar ratio of concentrated sulfuric acid to hydrogen peroxide in a system to be 1:1, mixing and stirring in a continuous reaction leaching tank for 2 hours to obtain a mixture, wherein the mixture comprises a manganese sulfate solution and waste residues containing lead and silver, the mixture is filtered and concentrated by a ceramic membrane to obtain a filtered manganese sulfate solution and a filtered bottom concentrated solution, and the filtered bottom concentrated solution is subjected to pressure filtration by a membrane filter press to obtain waste residues A;
(2) and (3) mixing the filtered manganese sulfate solution according to the manganese content of 1: 0.8 adding manganese dioxide powder, slowly adding high-concentration ammonia water, reacting in a closed stator-rotor reactor for 2 hours until the pH value reaches 7.0 to generate slurry containing manganous manganic oxide, heating the slurry containing the manganous manganic oxide to 60 ℃, filtering the slurry through a ceramic membrane to obtain filtrate B and bottom manganous manganic oxide thick slurry, pumping the bottom manganous manganic oxide thick slurry into a washer through a slurry pump, washing the bottom manganous manganic oxide thick slurry with deionized water, pumping the bottom manganous manganic oxide thick slurry into a spray drying tower through a diaphragm pump, drying purified fuming furnace tail gas, and metering and packaging the dried manganous manganic oxide from the bottom of the tower through a high-magnetism demagnetizing device and a rotor flow meter;
(3) adding ammonium bicarbonate into the filtrate B, enabling unreacted manganese sulfate in the filtrate to generate manganese carbonate precipitate, filtering to obtain a purified ammonium sulfate solution, pumping the purified ammonium sulfate solution into a slurry preparation tank, adding lime milk, flowing into an ammonia still, evaporating ammonia at the temperature of 90 ℃ by using the waste heat of a fuming furnace, absorbing ammonia gas discharged from the top of the tower by using cold water of a hydrogen condensation tower to prepare high-concentration ammonia water for recycling, performing filter pressing on the deaminated slurry to separate solid from liquid of calcium sulfate, and performing multi-effect evaporation on the separated liquid to prepare deionized water for recycling;
(4) waste residue A is prepared by mixing the following raw materials in a weight ratio of 1:1 adding coke, adding into a fuming furnace to smelt lead-silver alloy, cooling and crystallizing the flue gas by an ammonia still to obtain lead crystals and fuming furnace tail gas, and recycling the fuming furnace tail gas after belt type dust removal and purification, and discharging into the atmosphere.
Preferably, the concentration of the concentrated sulfuric acid in the step (1) is 93%.
Preferably, the concentration of the hydrogen peroxide in the step (1) is 25 to 35 percent.
Preferably, the manganese content of the mixture in the step (1) is more than 40 g/l.
Preferably, the concentration of the high-concentration ammonia water in the step (2) is 30-40%.
Preferably, the volume ratio of the ammonium sulfate solution to the lime milk in the step (3) is 1: 1.
preferably, the waste residue A in the step (4) is lead-rich slag.
According to the technical scheme, the method for producing the trimanganese tetroxide and co-producing the lead-silver alloy provides technical support for high-quality development of the electrolytic manganese industry, the trimanganese tetroxide is a precursor material produced by the current lithium manganate battery, and along with rapid development of the battery industry and rising of the price of electrolytic manganese in recent years, the trimanganese tetroxide market has a high-price and difficult-to-demand situation.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The invention aims to provide a process method for producing battery-grade trimanganese tetroxide and co-producing lead-silver alloy by utilizing electrolytic manganese anode slag, which realizes high-valued comprehensive utilization of the electrolytic manganese anode slag and high-quality development of the manganese industry.
The theory of the invention is as follows:
MnO2+H2SO4+H2O2＝MnSO4+2H2O+O2
2MnSO4+MnO2+4NH3+4H2O＝Mn3O4+2(NH4)2SO4+2H2O
the invention comprises the following steps
(1) Obtaining electrolytic manganese anode slag, and mixing the anode slag with the solid-liquid ratio of 1: 10, adding deionized water to prepare slurry, adding 93% concentrated sulfuric acid and 25% -35% hydrogen peroxide to enable the molar ratio of concentrated sulfuric acid to hydrogen peroxide in the system to be 1:1, mixing and stirring the mixture in a continuous reaction leaching tank for 2 hours to obtain a mixture, wherein the mixture comprises a manganese sulfate solution and waste residues containing lead and silver, the manganese content of the mixture is more than 40g/l, filtering the mixture by a ceramic membrane to obtain the filtered manganese sulfate solution and a bottom concentrated solution, and performing filter pressing on the bottom concentrated solution by using a membrane filter press to obtain lead-rich residues;
(2) and (3) mixing the filtered manganese sulfate solution according to the manganese content of 1: 0.8 adding manganese dioxide powder, slowly adding 30-40% high-concentration ammonia water, reacting in a closed stator-rotor reactor for 2 hours until the pH value reaches 7.0, completely reacting to generate slurry containing manganous manganic oxide, heating the slurry containing manganous manganic oxide to 60 ℃, filtering and thickening the slurry through a ceramic membrane to obtain slurry containing unreacted manganese sulfate filtrate and bottom manganous manganic oxide, pumping the bottom manganous manganic oxide into a washer through a slurry pump, washing the bottom manganous manganic oxide with deionized water, pumping the bottom manganous manganic oxide into a diaphragm pump spray drying tower, drying purified fuming furnace tail gas, and metering and packaging the dried manganous manganic oxide from the bottom of the tower through a high magnetism removing device and a rotor flow meter;
(3) adding ammonium bicarbonate into the unreacted manganese sulfate filtrate to enable the unreacted manganese sulfate in the filtrate to generate manganese carbonate precipitate, and filtering to obtain a purified ammonium sulfate solution, wherein the volume ratio of the purified ammonium sulfate solution is 1:1, pumping the mixture into a slurry preparation tank, adding lime milk, flowing into an ammonia still, evaporating ammonia at the temperature of 90 ℃ by using the waste heat of a fuming furnace, absorbing the ammonia gas discharged from the top of the tower by using cold water of a hydrogen condensation tower to prepare high-concentration ammonia water for recycling, wherein the ammonia water can be directly used for the step (2), the ammonia still is clean and environment-friendly and does not cause resource waste, the slurry after deamination is subjected to filter pressing to separate solid and liquid of calcium sulfate, the solid of calcium sulfate is dried, crushed and packaged and can be used for sale, the separated liquid is subjected to multiple-effect evaporation to prepare deionized water for recycling, and the deionized water can be directly used for the process of using the deionized water in the step (1) and the step (2);
(4) waste residue A is prepared by mixing the following raw materials in a weight ratio of 1:1, adding coke, adding a fuming furnace to smelt lead-silver alloy, cooling and crystallizing the flue gas through an ammonia still to obtain lead crystals and fuming furnace tail gas, and recycling the fuming furnace tail gas after belt type dust removal and purification, wherein the fuming furnace tail gas can be directly taken to be applied to the step (2) for drying trimanganese tetroxide to reach waste guarantee and be discharged into the atmosphere.
The invention uses sulfuric acid and hydrogen peroxide to leach electrolytic manganese anode slag for reaction to generate manganese sulfate solution, and then removes lead-rich slag for standby application by filter pressing. Filtering the filtrate by a ceramic membrane, adding industrial-grade manganese dioxide, stirring, slowly adding concentrated ammonia water, reacting for two hours, heating to 60 ℃, filtering, washing filter residues by water, spray drying, demagnetizing and packaging to obtain a finished product of trimanganese tetroxide, adding lime milk into the filtrate to deaminate to prepare ammonia water, carrying out dense filter pressing and drying on the emulsion to generate calcium sulfate solid, drying, crushing, packaging and selling, wherein the calcium sulfate solid is used for the building industry without causing resource waste, and the filtrate is subjected to multi-effect evaporation to prepare deionized water for the prior process steps. Adding the lead-rich slag into coke, and smelting and recovering lead and noble metals by using a fuming furnace.
Claims (7)
1. The method for producing the trimanganese tetroxide and the co-production of the lead-silver alloy is characterized by comprising the following steps:
(1) obtaining electrolytic manganese anode slag, and mixing the anode slag with the solid-liquid ratio of 1: 10, adding deionized water to prepare slurry, adding concentrated sulfuric acid and hydrogen peroxide to enable the molar ratio of concentrated sulfuric acid to hydrogen peroxide in a system to be 1:1, mixing and stirring in a continuous reaction leaching tank for 2 hours to obtain a mixture, wherein the mixture comprises a manganese sulfate solution and waste residues containing lead and silver, the mixture is filtered and concentrated by a ceramic membrane to obtain a filtered manganese sulfate solution and a filtered bottom concentrated solution, and the bottom concentrated solution is subjected to pressure filtration by a membrane filter press to obtain waste residues A;
(2) and (3) mixing the filtered manganese sulfate solution according to the manganese content of 1: 0.8 adding manganese dioxide powder, slowly adding high-concentration ammonia water, reacting in a closed stator-rotor reactor for 2 hours until the pH value reaches 7.0, completely reacting to generate slurry containing manganous manganic oxide, heating the slurry containing the manganous manganic oxide to 60 ℃, filtering the slurry through a ceramic membrane to be dense to obtain filtrate B and bottom manganous manganic oxide thick slurry, pumping the bottom manganous manganic oxide thick slurry into a washer through a slurry pump, washing the bottom manganous manganic oxide thick slurry with deionized water, pumping the bottom manganous manganic oxide thick slurry into a spray drying tower through a diaphragm pump, drying purified fuming furnace tail gas, and metering and packaging the dried manganous manganic oxide from the bottom of the tower through a high-magnetism demagnetizing device and a rotor flow meter;
(3) adding ammonium bicarbonate into the filtrate B, enabling unreacted manganese sulfate in the filtrate to generate manganese carbonate precipitate, filtering to obtain a purified ammonium sulfate solution, pumping the purified ammonium sulfate solution into a slurry preparation tank, adding lime milk, flowing into an ammonia still, evaporating ammonia at the temperature of 90 ℃ by using the waste heat of a fuming furnace, absorbing ammonia gas discharged from the top of the tower by using cold water of a hydrogen condensation tower to prepare high-concentration ammonia water for recycling, performing filter pressing on the deaminated slurry to separate solid from liquid of calcium sulfate, and performing multi-effect evaporation on the separated liquid to prepare deionized water for recycling;
(4) mixing the waste residue A with the following raw materials in a weight ratio of 1:1, adding coke, adding the coke into a fuming furnace to smelt lead-silver alloy, cooling and crystallizing smoke through an ammonia still to obtain lead crystals and fuming furnace tail gas, and recycling the fuming furnace tail gas after belt type dust removal and purification and discharging the smoke into the atmosphere.
2. The method for producing trimanganese tetroxide from electrolytic manganese anode slag according to claim 1, wherein the concentration of concentrated sulfuric acid in the step (1) is 93%.
3. The method for producing trimanganese tetroxide by using electrolytic manganese anode slag as claimed in claim 1, wherein the concentration of hydrogen peroxide in the step (1) is 25% -35%.
4. The method for producing trimanganese tetroxide from electrolytic manganese anode slag according to claim 1, wherein the manganese content of the mixture in the step (1) is more than 40 g/l.
5. The method for producing mangano-manganic oxide by using the electrolytic manganese anode slag as claimed in claim 1, wherein the concentration of the high-concentration ammonia water in the step (2) is 30-40%.
6. The method for producing trimanganese tetroxide by using electrolytic manganese anode slag according to claim 1, wherein the volume ratio of the ammonium sulfate solution to the lime milk in the step (3) is 1: 1.
7. the method for producing manganomanganic oxide by using electrolytic manganese anode slag as claimed in claim 1, wherein the waste residue A in the step (4) is lead-rich slag.
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| CN202111657320.0A CN114655987A (en) | 2021-12-31 | 2021-12-31 | Method for producing mangano-manganic oxide and co-producing lead-silver alloy |
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| CN202111657320.0A CN114655987A (en) | 2021-12-31 | 2021-12-31 | Method for producing mangano-manganic oxide and co-producing lead-silver alloy |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN108754145A (en) * | 2018-05-30 | 2018-11-06 | 宁夏天元锰业有限公司 | The technique of valuable metal in a kind of recycling electrolytic manganese anode mud |
| CN110016562A (en) * | 2019-04-23 | 2019-07-16 | 重庆大学 | A kind of method of lead in removing electrolytic manganese anode mud |
| CN213977836U (en) * | 2020-12-23 | 2021-08-17 | 贵州大龙汇成新材料有限公司 | System for producing manganese sulfate by electrolytic manganese anode slag |
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2021
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| JPH05208824A (en) * | 1992-01-28 | 1993-08-20 | Kansai Coke & Chem Co Ltd | Production of trimanganese tetroxide |
| CN101691633A (en) * | 2009-10-12 | 2010-04-07 | 湖南广义科技有限公司 | Method for innocent treatment and comprehensive utilization of manganese slag |
| CN102730762A (en) * | 2012-06-26 | 2012-10-17 | 深圳市新昊青科技有限公司 | Low BET ball-type manganic manganous oxide and its preparation method |
| CN108754145A (en) * | 2018-05-30 | 2018-11-06 | 宁夏天元锰业有限公司 | The technique of valuable metal in a kind of recycling electrolytic manganese anode mud |
| CN110016562A (en) * | 2019-04-23 | 2019-07-16 | 重庆大学 | A kind of method of lead in removing electrolytic manganese anode mud |
| CN213977836U (en) * | 2020-12-23 | 2021-08-17 | 贵州大龙汇成新材料有限公司 | System for producing manganese sulfate by electrolytic manganese anode slag |
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